BIOMASS CONVERSION TO BIO-BASED PRODUCTS
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Creative
Resourceful
Excellent
Green
Prof. Ir. Dr. Nor Aishah Saidina Amin
Chemical Reaction Engineering Group (CREG),
Faculty of Chemical & Energy Engineering,
University Technology Malaysia, Johor Bahru,
Malaysia.
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PRESENTATION OUTLINE
Introduction
Biomass Opportunity & Biobased Chemical Market
Building Block Chemical from Biomass
Lignin for Carbon Cryogel Production
Properties of Carbon Cryogel
Potential of Carbon Cryogel as Catalyst for Biodiesel Production
Lignocellulosic Biomass Pretreatment
Ozonolysis Pretreatment
Potential Uses from Ozonolysis Pretreated Biomass
Sugars Derived Holocellulose for Levulinic Acid Production
Acid Hydrolysis and Dehydration for LA Production
Modified HY Zeolite & Functionalized Ionic Liquid as Catalyst
Conclusions
Acknowledgement
Malaysia: ~11% gross national
income (GNI) from
agriculture sector
80 million
dry
tonnes
(2010)
110 million
dry tonnes
(2020)
Oil palm Rubber Kenaf Paddy
Source: National Biomass Strategy 2020
BIOMASS OPPORTUNITY
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BIO-BASED CHEMICAL MARKET
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Werpy et al., 2004.innovative ● entrepreneurial ● global
BUILDING BLOCK CHEMICALS
FROM BIOMASS
HO
OH
O
O
Succinic acid
HO
OH
O
O
Fumaric acid
HO
OH
OHO
OMalic acid
O
HO OH
O O
2,5-furan dicarboxylic acid
HO OH
O
3-hydroxy propionic acid
O
OH
O
OH NH2
Aspartic acid
HO
OH
O
O
CH3
Itanoic acid
HO
CH3
O
O
Levulinic acid
HO OH
OH
Glycerol
HO OH
OH OH
OH
Xylitol
OO
OH
3-hydroxybutyrolactone
HO OH
O O
NH2
Glutamic acid
HO
OH
O
O
OH OH
OHOH
Glucaric acid
HO
OH
OH
OH
OH
OH
Sorbitol
Lignocellulosic Biomass
Pretreatment
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BIOMASS TO WEALTH INDUSTRY
BIOMASS
• Consist of cellulose, hemicellulose, lignin
• Limitation: lignin compound
PRETREATMENT
• degrade lignin
• Improve physical properties
• Increase holocelluloseaccessibility
BIO-BASED PRODUCT
• Convert sugars to valuable added product
GAP!!!
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BIOMASS PRETREATMENT METHODS
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Method Advantages Disadvantages
Alkali • High glucose recovery
• High solubility of hemicellulose
• Technology maturity for commercialization
• Corrosive
• Non-environmental friendly
Acid • Lower temperature and pressure
• Substrate rich in cellulose and xylan
• Corrosive
• non-environmental friendly
Hydrothermal • Only uses water for reaction medium
• Solubilize hemicellulose
• operated at high pressure
and temperature
• Lignin is remained in
sample
Steam
Explosion
• Limited chemicals are used except water
• Avoid excessive degradation of
monosaccharides
• Minimum corrosion of equipment
• Economical problem (high
operating cost)
• Inhibitor generation and
complex downstream
process
BIOMASS PRETREATMENT METHODS
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Method Advantages Disadvantages
Ionic Liquid • Tunability
• High thermal stability
• Low volatility
• Much effort needed to make
the method commercially viable
Microwave-
assisted
• Shorter time
• Increases pretreatment selectivity
• Decreases the pretreatment energy
output
• Enhances enzymatic efficiency
• Involve corrosive chemical
• Much effort to make the MW
pretreatment commercially
viable
• High cost
Ozonolysis • Ambient operating condition
• High lignin degradation without affecting
the cellulose component
• Substrate rich in cellulose and xylan
• No toxic waste produce
• High cost ozone production
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Constituents Composition (wt%)
Cellulose 30-31
Hemicellulose 20-24
Lignin 18-25
Ash 3-5
OIL PALM FRONDS (OPF)
Physical Properties
Moisture content 10 wt.%
Crystalinity 28-34 %
Surface area 1.0029 m2/g
Pore volume 0.0029 cm3/g
Pore diameter 11.57 nm
OZONOLYSIS SYSTEM FOR
OPF PRETREATMENT
Water film
Lignin film
OPF Surface
Treated OPF surface
HOW THE OZONE WORKS?
OPF surface
Exposure
cellulose surface
O3 O3
Kraft Lignin
Break AIL to ASL
Bio-based chemical
derived sugars
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OBSERVATION FROM OZONOLYSIS
0 min (15-20) min (30-40)min
>50min End of reaction
Washing with NaOH
Before treatment
After washing and filtration
After Drying
End
PROTOTYPE FOR
OZONOLYSIS PRETREATMENT
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Electrical
Motor
Ozone
Outlet
Ozone
Inlet
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OZONOLYSIS PRETREATMENT
OF OPF
LignocellulosicBiomass
Cellulose Hemicellulose Lignin
Ozonolysis
Sample CodedMoisture
content (wt.%)
Particle
size (mm)
Reaction time
(hr)
Ozone flowrate
(mL/min)
Ozone
concentration
(wt.%)
Untreated
(UTP)10 0.8 - - -
R3 30 0.8 1 30 40
R4 70 0.8 1 60 20
R5 30 0.3 2 60 20
R6 70 0.3 2 30 40
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PRETREATED OPF
UntreatedLignin degrade
>90%
highly
fibrillar,
intact
morphology
structure
structure is
totally
disrupted
Lignin degrade:
medium
Lignin degrade:
low
structure is
slightly
disrupted
structure is
slightly
disrupted
FESEM - Morphology
PRETREATED OPF
Plasma cell wall
Microfibril Strand
Cellulose Rosette
UNTREATED OPF
PRETREATED OPF
Breakage of
cell wall
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PRETREATED OPF
0
10
20
30
40
50
60
70
80
90
100
110
10 15 20 25 30 35 40 45 50
Inte
nsi
ty (
a.u
)
2-Theta
UT P
R4
R5
R6
Lignin
Degradation
(%)
Crytalinity
Index (CrI)
(%)
BET Surface
Area
(m2/g)
Pore
Diameter
(nm)
Pore
Volume
(x 10-3 cm3/g)
n/a 36.1 1.03 11.40 2.93
90.15 51.9 0.74 11.10 2.05
39.02 52.1 1.07 98.74 2.65
1.83 50.1 1.00 11.01 2.76
treated sample increased the
intensity of crystal structure
higher lignin degradation (R4)
showed the highest intensity but
not CrI
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POTENTIAL USES FROM
PRETREATED OPF
0
2
4
6
8
10
12
14
16
Cellulose Untreated OPF Treated OPF
LA
yie
ld (
wt%
) per
feedsto
ck
Sugars Derived
Holocellulose for
Levulinic Acid (LA)
Production
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PRODUCTS FROM BIOMASS
PRETREATMENT – POTENTIAL USES
LignocellulosicBiomass
Cellulose Hemicellulose Lignin
Ozonolysis
Sugars
5-hydroxymethyl furfural (5-HMF)
Levulinic Acid (LA)
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LEVULINIC ACID – BUILDING BLOCK
CHEMICAL
Fuels additives
Flavoring & fragrance
Pharmaceutical agentsResins
Polymers
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OHOH2C CHO
H3C COOH
O
+ HCOOH
H+
H+
levulinic acid
O
OH
OH
OH
OH
CH2OH
glucose
formic acid
CH2OH
OH
OH OHHOH2C
fructose
isomerization
rehydration
dehydrationHMF
BIOMASS CONVERSION TO LA
OHO
OH
OH
OH
OH
OO
OH
OH
OH
O
OH
OH
OH
O
Cellulose Glucose
OPF
Biomass
dissolution /
pretreatement
Cellulose
hydrolysis
Bronsted Acid
Bronsted AcidLewis Acid
ACID CATALYSTS FOR LEVULINIC ACID
PRODUCTION
Iron Modified HY Zeolite
(Fe/HY) catalyst
Functionalized Ionic
Liquid (FIL) catalysts
Catalysts preparation
Catalysts
characterization
Optimization
Catalyst screening
Levulinic acid production
from glucose
Levulinic acid production
from OPF
Kinetic study
Fe/HY ZEOLITE – XRD, FTIR
5 10 15 20 25 30 35 40 45 50
Inte
nsi
ty
2 theta (o)
5% Fe/HY
10% Fe/HY
15% Fe/HY
HY zeolite
XRD patterns of HY zeolite and Fe/HY zeolite
catalysts.
4000 3600 3200 2800 2400 2000 1600 1200 800 400
15% Fe/HY
10% Fe/HY
5% Fe/HY
HY zeolite
Ab
so
rba
nce
Wavenumber (cm-1)
FTIR spectra of HY zeolite and Fe/HY zeolite
catalysts
• XRD patterns of Fe/HY zeolite matched
with parent HY zeolite.
• Modification has no obvious effect
• HY zeolite structure remained intact
• No significant band shift from Fe/HY
zeolites spectra
Ramli et al., App Cat B, 2015;163:487-498
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Fe/HY ZEOLITE – N2 PHYSISORPTION
Catalysts SBET a
(m2/g)
Smeso b
(m2/g)
Smicroc
(m2/g)
Vporesd
(cm3/g)
Vmesoe
(cm3/g)
Vmicro f
(cm3/g)
Dmeang
(nm)
Dmesoh
(nm)
Dmicroi
(nm)
HF j
HY zeolite 829.5 76.4 753.1 0.369 0.082 0.287 1.78 5.86 0.54 0.0716
5% Fe/HY 598.9 122.5 476.5 0.279 0.092 0.187 1.83 4.33 0.53 0.1371
10% Fe/HY 549.3 133.6 415.8 0.265 0.098 0.167 1.89 3.77 0.52 0.1532
15% Fe/HY 522.1 145.0 377.1 0.263 0.109 0.154 1.98 3.62 0.52 0.1626
Surface area and porosity of HY zeolite and Fe/HY zeolite catalysts
• Impregnation - decreased surface area and pore
volume
• Presence of Iron oxide blocked some of the pores
• Type I isotherm – microporosity of
samples
Ramli et al., App Cat B, 2015;163:487-498
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Fe/HY ZEOLITE – TPD, FTIR PYRIDINE
0 200 400 600 800
Temperature (oC)
Inte
nsi
ty (
a.u
)
Fe/HY 5%
HY zeolite
Fe/HY 10%
Fe/HY 15%
1560 1540 1520 1500 1480 1460 1440 1420
Ab
sorb
ance
Wavenumber (cm-1)
B L
15% Fe/HY
5% Fe/HY
10% Fe/HY
HY zeolite
NH3-TPD profiles of catalysts FTIR spectra of pyridine absorbed on catalysts
• Impregnation of FeCl3 increase the
acidity
Catalysts Total acidity
(mmol/g)
Number of acid
sites (µmol/m2)
HY zeolite 1.58 1.91
5% Fe/HY 2.81 4.69
10% Fe/HY 2.68 4.88
15% Fe/HY 2.12 4.06
• Fe/HY zeolites has higher Lewis acid
sites
Ramli et al., App Cat B, 2015;163:487-498
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Fe/HY ZEOLITE – GLUCOSE TO
LEVULINIC ACID
120 140 160 180 2000
10
20
30
40
50
60
70(a)
Pro
du
ct
yie
ld (
%)
Reaction temperature (oC)
Levulinic acid
Formic acid
5-HMF
120 140 160 180 2000
10
20
30
40
50
60
70
Pro
duct
yie
ld (
%)
Reaction temperature (oC)
Levulinic acid
Formic acid
5-HMF
(b)
120 140 160 180 2000
10
20
30
40
50
60
70
Pro
duct
yie
ld (
%)
Reaction temperature (%)
Levulinic acid
Formic acid
5-HMF
(c)
Product yields versus reaction temperature at 3 h of reaction time for
5% Fe/HY zeolite (a), 10% Fe/HY zeolite (b), and 15% Fe/HY
zeolite (c) catalysts.
• Highest LA yield at 180 C
• 10% Fe/HY zeolite - highest catalytic performance
10% Fe/HY
• High performance – high no of acid sites,
appropriate ratio of Bronsted to Lewis acid
5% Fe/HY
15% Fe/HY
Ramli et al., App Cat B, 2015;163:487-498
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FUNCTIONALIZED IONIC LIQUID
Cation
Drying
1-butyl-3-methyl imidazolium
tetrachloroferrate
[BMIM][FeCl4]
1-sulfonic acid-3-methyl imidazoliumchloride [SMIM][Cl]
1-sulfonic acid-3-methyl imidazoliumtetrachloroferrate
[SMIM][FeCl4]
Anion
Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121.
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FIL - ACIDITY
Pyridine-FTIR spectra of FIL catalysts.
• [SMIM][FeCl4] consisted of both Lewis and
Bronsted acid sites
• Bronsted – sulfonic acid group in cation
• Lewis – FeCl4 in anion
Acidity of FIL
[SMIM][FeCl4]
[SMIM][Cl]
[BMIM][FeCl4]
N N
Cl
FeCl3.6H2O
N N+ 6H2O
+
FeCl4
+
+
N N+ SO3HCl
N N
SO3H
Cl
Cl
+ FeCl3.6H2O
N N
SO3H
+
+
FeCl4
CH2Cl2
(a)
(b)
(c)
N N
SO3H+
+
6H2O+
N N
Cl
FeCl3.6H2O
N N+ 6H2O
+
FeCl4
+
+
N N+ SO3HCl
N N
SO3H
Cl
Cl
+ FeCl3.6H2O
N N
SO3H
+
+
FeCl4
CH2Cl2
(a)
(b)
(c)
N N
SO3H+
+
6H2O+
N N
Cl
FeCl3.6H2O
N N+ 6H2O
+
FeCl4
+
+
N N+ SO3HCl
N N
SO3H
Cl
Cl
+ FeCl3.6H2O
N N
SO3H
+
+
FeCl4
CH2Cl2
(a)
(b)
(c)
N N
SO3H+
+
6H2O+
1-butyl-3-methyl imidazolium tetrachloro ferrate
1-sulfonic acid-3-methyl imidazolium chloride
1-sulfonic acid-3-methyl imidazolium
tetrachloro ferrate
[BMIM][FeCl4]
[SMIM][Cl]
[SMIM][FeCl4]
Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121
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FIL – GLUCOSE TO LEVULINIC ACID
1 2 3 4 50
5
10
15
20
25
30
Levulin
ic a
cid
yie
ld (
%)
Reaction time (h)
1 2 3 4 50
5
10
15
20
25
30
Levu
linic
acid
yie
ld (
%)
Reaction time (h)
1 2 3 4 50
15
30
45
60
75
Levu
linic
acid
yie
ld (
%)
Reaction time (h)
LA yield using [BMIM][FeCl4], [SMIM][Cl], [SMIM][FeCl4] as a
catalyst ■ 170 °C, ▲150 °C, ●130 °C, ×110 °C. 10g FIL, 10 ml H2O
[BMIM][FeCl4]
[SMIM][Cl]
• [SMIM][FeCl4] - highest catalytic performance
• High activity – high acidity comprised of both
Bronsted and Lewis acid sites [SMIM][FeCl4]
Ramli et al., J. Mol. Cat. A: Chem. 407, 113-121
Fe/HY – GLUCOSE TO LEVULINIC ACIDGlucose
(G) Levulinic acid
Humins and unidentified soluble products
k1
k2 k4
k35-hydroxymethyl furfural (H)
Reaction scheme for glucose conversion to LA
Key Steps Reaction
1. Glucose conversion to 5-HMF
2. Glucose decomposition to
humins
3. 5-HMF conversion to LA
4. 5-HMF decomposition to
humins
(Eq. 1)
(Eq. 2)
𝑅𝐺 = (𝑘1 + 𝑘2)𝐶𝐺
𝑅𝐻 = 𝑘3 + 𝑘4 𝐶𝐻
−𝑑𝐶𝐺
𝑑𝑡= 𝑘1 + 𝑘2 𝐶𝐺
𝑑𝐶𝐻
𝑑𝑡= 𝑘1𝐶𝐺 − 𝑘3 + 𝑘4 𝐶𝐻
𝑑𝐶𝐿𝐴
𝑑𝑡= 𝑘3𝐶𝐻
(Eq. 3)
(Eq. 4)
(Eq. 5)
Ramli et al., Chem. Eng. J. 283, 150-159.
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Fe/HY – GLUCOSE TO LEVULINIC ACID
0 50 100 150 200 250
0.0
1.5
3.0
4.5
6.0 Glucose conversion
-ln
(1
-X)
Reaction time (min)
0 50 100 150 200 250
0.0
1.5
3.0
4.5
6.0
-ln
(1
-X)
Reaction time (min)
5-HMF conversion
-ln(1-X) versus time for (a) glucose conversion and (b)
5-HMF conversion using 10% Fe/HY zeolite. ■ 120
°C, ▲ 140 °C, ● 160 °C, * 180 °C, ○ 200 °C.
- 10% Fe/HY zeolite
- 120 to 200 °C from 0 to 240 min
-Linearity of -ln(1-X) versus time
- 1st order reaction
Ramli et al., Chem. Eng. J. 283, 150-159.
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FIL – GLUCOSE TO LEVULINIC ACID
0 50 100 150 200 250 300
0.0
1.5
3.0
4.5
6.0 Glucose conversion
-ln (
1-X
)
Time (min)
0 50 100 150 200 250 300
0.0
1.5
3.0
4.5
6.0
-ln
(1
-X)
Time (min)
5-HMF conversion
Effect -ln(1-X) versus time for glucose conversion and 5-
HMF conversion using [SMIM][FeCl4].
■ 110 °C, ▲ 130 °C, ● 150 °C, * 170 °C.
- [SMIM][FeCl4]
-110 to 170 °C from 0 to 300
min
-Linearity of -ln(1-X) versus
time
- 1st order reaction
Ramli et al., Chem. Eng. J. 283, 150-159.
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PRESENTATION OUTLINE
Presentation OutlineProposed model Reaction conditions Ea (kJ.mol-1) Reference
120 – 200 °C10% Fe/HY zeolite
Ea1 = 66
Ea2 = 76
Ea3 = 68
Ea4 = 67
This study
110 – 170 °C[SMIM][FeCl4]
Ea1 = 50
Ea2 = 34
Ea3 = 26
Ea4 = 44
This study
180 – 280 °CNon catalyzed
Ea1 = 108
Ea2 = 136
Ea3 = 89
Ea4 = 109
Ea5 = 131
(Jing and LÜ, 2008)
170 – 210 °CH2SO4
Ea1 = 86
Ea2 = 57
Ea3 = 209
(Chang et al., 2006)
140 – 180 °CHCl
Ea1 = 160
Ea2 = 51
Ea3 = 95
Ea4 = 142
(Weingarten et al.,
2012)
140 – 180 °C[C2OHMIM][BF4]
Ea1 = 56 (Qu et al., 2012)
80 – 120 °CCrCl3 in [AMIM][Cl]
Ea1 =135 (Zhang et al., 2014)
Glucose 5-HMF LA
Humins Humins
1
2 4
3
Glucose 5-HMF LA
Humins Humins
1
2 4
3
Glucose 5-HMF LA
Humins Humins
1
2 4
3
Decomposition
product
5
Glucose 5-HMF LA1
3
2
Humins
Glucose 5-HMF LA
Humins Humins
1
2 4
3
Glucose 5-HMF1
Glucose 5-HMF1
Introduction of catalyst (Fe/HY @
[SMIM][FeCl4]) has accelerated the
reaction, consequently lowering the Ea
LEVULINIC ACID PRODUCTION
FROM BIOMASS FEEDSTOCKS
BiomassCellulose
content (%)Catalyst
LA yield (%) Efficiency
(%)Biomass Theoretical
Oil palm fronds 45.2 Fe/HY zeolite 19.6 32.1 61.1
Oil palm fronds 45.2 [SMIM][FeCl4] 24.8 32.1 77.3
Water hyacinth [1] 26.3 H2SO4 9.0 18.7 48.2
Wheat straw [5] 40.4 H2SO4 19.9 28.7 68.8
Rice straw [18] 46.1 S2O82-/ZrO2-SiO2-Sm2O3 22.8 32.7 70.0
Empty fruit bunch
[17]
41.1 Cr/HY zeolite 15.5 29.2 53.2
Sorghum grain [19] 73.8 H2SO4 32.6 52.4 62.2
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Fe/HY AND FIL REUSABILITY FOR
LEVULINIC ACID PRODUCTION
0
5
10
15
20
25
20
30
40
50
60
70
1 2 3 4 5
LA
yie
ld f
rom
glu
cose (
%)
Run
Glucose (Fe/HY) Glucose ([SMIM][FeCl])
OPF (Fe/HY) OPF ([SMIM][FeCl4])
LA
yie
ld fro
m O
PF
(%)
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Lignin for
Carbon Cryogel Production
PRODUCTS FROM BIOMASS
PRETREATMENT – POTENTIAL USES
LignocellulosicBiomass
Cellulose Hemicellulose Lignin
Carbon Cryogel
Ozonolysis
Sugars
5-hydroxymethyl furfural (5-HMF)
Levulinic Acid (LA)
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CARBON CRYOGEL
Phenol / Resorcinol
Catalyst /
catalyst support
Carbon
gels Formaldehyde
+
Aerogel Cryogel Xerogel
Substituted phenol and formaldehyde derivatives can be used to
produce organic gels
Synthesis
from toxic
chemicals
Expensive
drying
process
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CARBON CRYOGEL
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Mix with furfural, EtOH,
acid sulfuric, distilled water
• Heat treatment at 90˚C
(silicone oil temp.), 0.5 h
• Solvent exchange with t-butanol
• Pre-frozen 24 h (refrigerator),
• dried at -60 ˚C, 8 h (condenser temp.)
Lignin
Solvent exchange and Freeze dried
Gels
Cryogel Characterization TGA
surface area, TPD, TGA,
FESEM Characterization
• Under nitrogen flow: 500˚C,5 h
Carbon Cryogel
Carbonization
CARBON CRYOGEL
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0
90
180
270
360
450
300 400 500 600 700
0
4
8
12
16
20
SB
ET (
m2/g
)
Acid
ity (m
mo
l/g)
Temperature (oC)
High total surface area and acidity
Optimum surface area and acidity
The optimum
temperature
EFFECT OF CARBONIZATION
TEMPERATURE ON CRYOGEL
CARBON CRYOGEL
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EFFECT OF CARBONIZATION
TIME ON CRYOGEL
High total surface area of 214 m2/g and total
acidity of 11.29 mmol/gSelected as optimum condition at 500 ˚C and 4 h
0
80
160
240
320
400
Acid
ity (m
mo
l/g)
SB
ET (
m2/g
)
1 2 3 4 50
4
8
12
16
20
Time (h)
The optimum time
CARBON CRYOGEL
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Thermal stability: Carbon cryogel > cryogel
20
40
60
80
100 Weig
ht lo
sses ra
te (w
t% m
in–1)
Weig
ht (w
t.%
)
Temperature (C)
0
1
2
3
4
5
6
200 400 600 8000
Cryogel
Carbon Cryogel
Volatilization
of moisture
Decomposition of SO3
& organic compound
Decomposition of lignin
CARBON CRYOGEL
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EFFECT OF CARBONIZATION
TEMPERATURE ON CRYOGEL
Carbon CryogelCryogel
500X 500X
50m 50m
• Size reduction after carbonization
Decomposition of organic compound during carbonization
Reduction & reconstructuring of functional group & carbon bonding
Surface area increased
CARBON CRYOGEL AS CATALYST
FOR LEVULINIC ACID ESTERIFICATION
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OH
O
O
O
O
O
EtOH H2O+ +
Levulinic Acid Ethyl Levulinate
Levulinic Acid Esterification with Ethanol to Ethyl Levulinate
Carbon
cryogel
CARBON CRYOGEL AS CATALYST
FOR LEVULINIC ACID ESTERIFICATION
innovative ● entrepreneurial ● globalRef.: [1,2] Fernandes et. al, App. Cat. A, 2012. 425: p. 199-204; [3] Nandiwale et. al, App. Cat. A, 2013. 460: p. 90-98; [4] Cirujano et. al,
Chem. Eng. Sci., 2015. 124: p. 52-60; [5] Yan et. al, Cat. Comm., 2013. 34: p. 58-63; [6] Pasquale et. al, Cat. Comm., 2012. 18: p. 115-120.
CatalystTime
(h)
Temperature
(°C)
Catalyst
loading (wt.%)
Molar ratio
(EtOH to LA)
Yield
(mol.%)Ref.
Amberlyst-15 5.0 70.0 2.5 5.0 55.0 [1]
SO4/SnO2 5.0 70.0 2.5 5.0 40.0 [2]
DPTA/DH-ZSM-5 4.0 78.0 25.0 6.0 82.0 [3]
UiO-66 8.0 78.0 1.82 15.0 94.0 [4]
H4SiW12O40/SiO2 6.0 75.0 51.0 18.0 67.0 [5]
40WD-S 10.0 78.0 107.7 (0.52) 64.0 76.0 [6]
Carbon Cryogel 3.0 150 25.0 20.0 84.0 This study
1 the data in wt.%2 the data in mol.%
CONCLUSIONS
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OZONOLYSIS PRETREATMENT
o High lignin degradation without affecting cellulose & hemicellulose component
o High sugar recovery
o High levulinic acid production from the ozonolysis pretreated biomass
SUGARS DERIVED HOLOCELLULOSE FOR LEVULINIC ACID PRODUCTION
o Fe/HY zeolite and functionalized ionic liquid as catalyst
o Bronsted and Lewis acids play roles in levulinic acid production
o Both catalyst can be reused for glucose and OPF conversion
o Glucose conversion to levulinic acid –1st order reaction, Ea lower and
comparable with other catalysts
LIGNIN FOR CARBON CRYOGEL PRODUCTIONo Lignin and furfural was used to produce carbon cryogel
o Carbon cryogel - high thermal stability, acidity, and surface area
o As catalyst for ethyl levulinate production from levulinic acid - 87.7 wt% yield
ACKNOWLEDGEMENT
Universiti Teknologi Malaysia for supporting the
project under the Research University Grant
Vote No. 03H48 and 07H14
innovative ● entrepreneurial ● global
Chemical Reaction Engineering Group (CREG),
Universiti Teknologi Malaysia
www.fche.utm.my/staf/noraishah
Tel: +6075535579, +60127165490
Email: [email protected]
innovative ● entrepreneurial ● global
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